Di [dihydrocarbylphosphito cyclohexyl (phenyl)] alkylidene



United States Patent 3,356,770 DI[DIHYDROCARBYLPHOSPHITO CYCLOHEXYL (PHENYL)]ALKYLHDENE Millard S. Larrison, Livingston, N.J., assignor, by mesne assignments, to First National Bank of Morgantown, Morgantown, W. Va, and Small Business Administration, Richmond, Va.

N0 Drawing. Filed dune 18, 1964, Ser. No. 376,202 4 Claims. (Cl. 260-330) ABSTRACT 9F THE DISCLOSURE Compounds having the formula where R and R are selected from the group consisting of alkyl, aryl and haloaryl and at least two of R and R are alkyl and Q is the divalent residue of a member of the group consisting of a dihydric phenol and a hydrogenated dihydric phenol are prepared by reacting 2 mols of a tertiary phosphite with one mol of the appropriate dihydric phenol or hydrogenated dihydric phenol. The compounds are useful as stabilizers for vinyl chloride resins and hydrocarbon polymers.

This application is a continuation-in-part of application Serial No. 366,891 filed May 12, 1964.

This invention relates to novel phosphite polymers.

In the thermoplastics industry, stabilization of the thermoplastic resins, e.g. polyvinyl chloride and polypropylene, by the use of barium, cadmium,-zinc, tin, lead and phosphite systems to prevent degradation from heat, light and weathering has contributed to the rapid growth into markets which were earlier closed to many plastics and has also greatly accelerated the rate of growth in many established areas.

The incorporation of liquid organic phosphates, e.g. see Leistner Patent 2,564,646, in stabilizing vinyl chloride resins has given spectacular improvements. However, in many cases the liquids are diflicult or impossible to use and as a result many attempts have been made to prepare the organic phosphite in solid form, preferably as a hard, frangible material that can be easily ground or powdered. These efforts have met with indiiferent successive in that the solids have been soft, waxy, unctuous, diflicult to maintain in finely divided condition and/ or susceptible to rapid hydrolysis.

It is an object of the present invention to make novel polymeric phosphites.

Another object is to make solid phosphites that can be incorporated into various plastic and elastic compositions as stabilizers.

An additional object is to prepare novel phosphite polymers having improved resistance to hydrolysis.

Still further objects and the entire scope of applicability of the present invention will become apparent from Patented Dec. 5, 1967 ice the detailed description given hereinafter; it should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

It has now been found that these objects can be attained by reacting a trihydrocarbyl phosphite or trihaloaryl phosphite with a dihydrie phenol, an aromatic dihydric alcohol or a hydrogenated dihydric phenol, Le. a dihydric alcohol resulting from the hydrogenation of a dihydric phenol (also called a hydrogenated bisphenol).

The reaction is preferably catalyzed with 0.l-5% by weight of the trihydrocarbyl phosphite of a dialkyl phosphite, a diaryl phosphite, a dihaloaryl phosphite or of an alkaline catalyst such as an alkali metal alc'oholate or phenolate. As examples of catalysts there can be used diphenyl phosphite, didecyl phosphite, phenyl decyl phosphite, di (2-methylphenyl) phosphite, di (4-dodecylphenyl) phosphite, di (2-chlorophenyl) phosphite, di (2,4- dimethylphenyl) phosphite, di (4-bromophenyl) phosphite, diethyl phosphite, dicyclohexyl phosphite, dioctadecyl phosphite, sodium phenolate, sodium decylate, potassium cresylate, sodium ethylate and sodium octadecanolate. Diphenyl phosphite and similar diaryl phosphites are the preferred catalysts.

It has been proposed previously to prepare polymeric pentaerythritol phosphite esters by reacting diphenyl pentaerythritol diphosphite and the like with a dihydric phenol or dihydric alcohol, Friedman Patent 3,053,878. The compounds of the present invention have superior hydrolytic stability to those of the Friedman patent.

As the trihydrocarbyl or trihaloaryl phosphite reactant there can be used triphenyl phosphite, tris (Z-methylphenyl) phosphite; tris (3-methylphenyl) phosphite, tris t-methylphenyl) phosphite, tris (Z-ethylphenyl) phosphite, tris (2-isopropylphenyl) phosphite, tris (4'dodecylphenyl) phosphite, tris (2,4-dimethylphenyl) phosphite, tris (2-chlorophenyl) phosphite, tris (2-bromophenyl) phosphite, tris (Z-fiuorophenyl) phosphite, tris (4-t-buty1- phenyl) phosphite, tris decyl phosphite, tris octyl phosphite, tris (alpha naphthyl) phosphite, diphenyl 4-methyl phenyl phosphite. The preferred phosphite reactants are triaryl phosphites, most preferably triphenyl phosphite.

As the diol reactant there can be used p-Xylylene glycol, m-Xylylene glycol, o-Xylylene glycol, bis (4-hydroxyphenyl) dimethyl methane (bisphenol A) and other di (hydroxyaryl) alkylidenes such as di (4-hydroxy-3- methylphenyl) dimethyl methane, di (4-hydroxy-3-methylphenyl) methyl methane, di (p-hydroxyphenol) methyl ethyl methane, di (4-hydroXy-3-methylphenyl) phenyl methane, di (4-hydroxyphenyl) methane, di (4-hydroxyphenyl) sulfone, di (4-hydroxypheny1) sulfide, di (4- hydroxyphenyl) sulfoxide, di (3-hydroxyphenyl) dimethyl methane, tetrachloro bisphenol A, tetrabromo bisphenol A, 4,4-methylene bis-(2-methyl-6-t-butylphenol), di(4- hydroxyphenyl) ether, resorcinol, hydroquinone, catechol, dihydroxydiphenyl, 4,4'-isopropylidene dicyclohexanol (also called bis (4-hydroxycyclohexyl) dimethyl methane or hydrogenated bisphenol A), 1,4-cyclohexane dimethanol, di (p-hydroxycycloheiryl) methyl ethyl methane, di .(4-hydroxycyclohexyl) methane, di (3hydroXy-' 3 cyclohexyl) dimethyl methane. The preferred dihydric compound is hydrogenated bisphenol A since it gives the best products.

To prepare the compounds of the present invention there are employed 0.5 to 1.5 mol of trihydrocarbyl phosphite or the like per mol of the dihydric compound, e.g. hydrogenated bisphenol A. Preferably there are used about 2 moles of trihydrocarbyl phosphite for 3 moles of diol, e.g. hydrogenated bisphenol A.

The reaction can be continued until a cross linked or highly branched polymer is formed. Preferably, however, the reaction is stopped while the product is still in the substantially linear or thermoplastic stage. When using the preferred reactants, namely hydrogenated bisphenol A and triphenyl phosphite, the reaction is stopped while the product has 63-68% phosphorus by weight. Thus, under the preferred conditions, the reaction is stopped when 65-75% of the theoretical amount of phenol derived from the triphenyl phosphite or the like is removed by distillation.

The reaction can be continued until 90% of the theoretical amount of phenol (i.e. from triphenyl phosphite) has been recovered but this is not preferred since it gives a cross linked thermosetting polymer. It is also possible tostop the reaction when only 50% of the theoretical amount of phenol has been recovered but in such case the thermoplastic polymer usually has not advanced to a stage giving optimum properties.

When using triphenyl phosphite and hydrogenated bisphenol A as the reactants, it has been observed that the greater the amount of phenol removed within the limits of 6.3 to 6.8% phosphorus content in the polymer formed, the less the color of the polymer. If the distillation is continued much beyond the point of 6.8% phosphorus content in the polymer, gel-like, i.e. cross linked materials, are formed rather than the preferred thermoplastic materials. The reaction is normally carried out with the aid of heat. The reaction can be continued as long as the phenol by-product is removed. Conveniently the phenol formed is removed by vacuum distillation, e.g. using a vacuum equivalent to mm. absolute pressure or less.

Many of these polymers are new materials. Thus the phosphite polymers from the hydrogenated dihydric phenols, e.g. hydrogenated bisphenol A are new.

Some of the polymers from dihydric phenols are closely related to the phosphite polymers disclosed in Nelson Patent 2,612,488. The procedure for making the dihydric phenol polymeric phosphites of Nelson, however, is more cumbersome than that used in the present invention and the use of phosphorus trichloride or the like also creates problems in obtaining a pure halogen free product. This is particularly true if the reaction is stopped prior to completion as is done. in the present invention to get the preferred thermoplastic polymers.

The Nelson procedure alsocannot be employed with the aromatic dihydric alcohols or the cycloaliphatic dihydric alcohols employed in the present invention because the alcohols react with phosphorus trichloride or the like to form organic halides. These in turn can react further to form phosphonates rather than the desired thermoplastic polymeric phosphites.

The products obtained according to the invention are brittle solid resins at room temperature. They can be readily ground for incorporation in an amount of 0.01 to into halogen containing resins, e.g. vinyl chloride resins, as stabilizers against heatand light. They can also be incorporated in an amount of 0.01 to 20% as stabilizers for hydrocarbon polymers such as polyethylene, polypropylene, ethylene-propylene copolymers (e.g. a 50:50 copolymer), polystyrene, acrylonitrile-butadiene-styrene terpolymer natural rubber, rubbery butadiene-styrene copolymer, polybutadiene, polyisobutylene, isobutylenebutadiene copolymer (butyl rubber) and the like. In some instances it is desirable to also incorporate a phenolic 4 antioxidant such as 2,2-methylene bis (4-methy1-6-t-butyl phenol) or 2,4,6-tri-t-butylphenol.

The products can also be used as antioxidants with barium, cadmium and zinc salts and synergistic activity has been noted in this connection. Thus there can be included 110% of salts such as barium-cadmium laurate, zinc stearate, cadmium 2-ethylhexoate, barium; nonylphenolate barium octylphenolate, barium stearate, zinc octoate in the antioxidant formulations.

The resins of the present invention can also be incorporated in an amount of 1 to 50% in other plastic materials to give improved flame and/or fire resistance. Thus they can be used to improve the fire resistance of cellulose, cellulose acetate, cellulose nitrate, cellulose acetate-butyrate, polystyrene, polyethylene, polypropylene and other polymeric monoolefins.

The resins of the present invention are also suitable to form cast or molded articles, e.g. disposable cups.

The initial heating for the reaction is preferably done slowly to avoid an explosion. After initial reaction at about to C., the reaction mass is heated above C., e.g. to C., and then vacuum distilled to remove the by-product phenol.

Unless otherwise indicated, all parts and percentages are by weight.

Example 1 Example 2 775 parts of triphenyl phosphite, 480 parts of hydrogenated bisphenol A and 10 parts of diphenyl phosphite were mixed and subjected to vacuum distillation. Terminal conditions were 208 C. and 29.5 inches of vacuum. 363 parts of phenol were removed from the system. The residue was a resinous polymer with a phosphorus content of 8.7%.

Example 3 341 parts of triphenyl phosphite, 240 parts of hydrogenated bisphenol A, and 6 parts of diphenyl phosphite were mixed and subjected to vacuum distillation. Terminal conditions were 216 C. and 29.5 inches of vacuum.

The residue was a resinous polymer with a phosphorus.

content of 8.4%.

Example 4 1860 parts of triphenyl phosphite, 2160 parts of hydrogenated bisphenol A and. 24 parts of diphenyl phosphite were mixed and subjected to vacuum distillation as in Example 3. 1112 parts of phenol distillate were removed. The residue was a hard amber'colored resin with a phosphorus content of 6.3%. The product is one of the preferred ones according to the invention and was compatible with and displayed anti-oxidant activity in stabilizing plastics, e.g. polyvinyl chloride, polyethylene, polypropylene, natural rubber and synthetic rubber. It was particularly effective in plastics when used in combination with conventional barium, zinc and cadmium stabilizers.

6 Example 5 inches of vacuum with a maximum still temperature of 178 C. 260 parts of phenol were removed, leaving a 62 Parts of triphenyl Phosphite were miXed With 41 liquid still residue which was a solid at room tempera- P of P- y y y The temperature Was main ture. The phosphorus content of this solid was 14.4%. tained in the temperature range, 100 to 110 C. for 20 5 minutes. The glycol dissolved slowly to give a clear vis- Example cous liquid. The temperature was then slowly raised to 341 parts f triphenyl phosphite, 150 parts of 1,4-cyand finally to 220 The j was finally clohexanedimethanol and 6 parts of diphenyl phosphite dlstlued under Hg l i at The final were mixed and subjected to vacuum distillation. Termi- Product was a hght colored butt 6 sohd at room ten? 10 nal conditions were 158 C. and 5 mm. Hg absolute presperature and had a phosphorus Content of sure. 210 parts of distillate were removed. The product was a clear white solid resinous polymer with a phos- Example 6 phorus content of 12%.

465 parts of triphenyl phosphite and 456 parts of bis- 15 Example 11 phenol A were mixed and subjected to vacuum distilla- 2160 parts of hydrogenated bisphenol A, 1860 parts tion. Terminal conditions were 200 C. and 5 mm. Hg of triphenyl phosphite and 24 parts of diphenyl phosphite absolute pressure. 385 parts of phenol were removed. were mixed and subjected to vacuum distillation. Termi- The product was a slightly yellow resinous polymer connal conditions were 205 C. and 29.5 inches of vacuum. taining 7.3% phosphorus. It was compatible in natural 1140 parts of distillate were removed. The still residue and synthetic rubbers, e.g. butadiene-styrene copolymer, was a clear solid resin with a phosphorus content of 6.4%. and in polyvinyl chloride and acrylonitrile-butadiene- This product is one of the preferred ones according to styrene resins. the invention.

Exampbe 7 As indicated a preferred series of solid phosphite resins 25 or polymers is prepared from triphenyl phosp'hite and hy- 240 parts of hydrogenated bi h l A 326 parts f drogenated bisphenol A in which the reactants are used triphenyl phosphite a d 4 parts of di h l phosphite 1n the molecular proportions to provide equal mols of were mixed and subjected to vacuum distillation. TermirePlaceable phenfjl and hydl'cxyl groups, 2 111013 of nal conditions were 210 C. and 29.5 inches of vacuum. trlphenyl Phosphlte and 3 mols of hydrogenated A total of 170 parts of phenol were removed by the disbisphenol A tillation. The product was a hard polymer with a phos- Varying F P of Phenol are removed from this Y phorus content of 8.17% tem to prov1de increased phosphorus content, increased molecular weights and decreased amounts of free hy- Examplg 8 droxyl groups. Thus by reacting the 2 mols of TI? with 3 mols of HBPA and stripping out 4 mols of phenol there 310 parts of triphenyl phosphite and 165parts of hyis formed a first polymer unit which has the following droquinone were mixed and subjected to vacuum distilformula (13H: 9H3 (EH3. C 5 4Q $113 0 CH3 0 CH3 lation' Terminal condition; welre 195') z mchgs This unit will be referred to hereinafter as a Triad and of vacuum Paris 0 p were rterllqve 2 the letter n used to designate the number of such Triad uct was a so 1 resinous po ymer con aming 0 p osunits in the Polymer molecule phorus E l 9 Thus when n is one as in the indicated formula the xamp 8 molecular weight is 964, the phosphorus content is 6.4% 165 parts of pyrocatechol was dried azeotropically by and the hydroxyl number is 116. distilling 100 parts of toluene from a mixture of the pyro- In the event that 4.5 mols of phenol are stripped out catechol and the toluene. To the dry pyrocatechol was (9 mols from 2 Triads) the formula of the product is added 310 parts of triphenyl phosphite. Phenol was then havinga molecular weight of 1834, phosphorus content removed from the system by distillation at 28.5 to 29.5 of 6.7% and a hydroxyl number of 91. I

If 4.67 mols of phenol are stripped out (14 mols from 3 Triads) the formula of the productis 8 Example 14 The procedure of Example 4 was repeated using 2112 3H YH (1H r H Y CH 3 JJH EH $11 H g e e e e e H H H H CH CH having a molecular weight of 2704, phosphorus content of 6.8% and hydroxyl number of 82.

parts of tris (4-methylphenyl) phosphite in place of the tri- The following table summarizes the products obtained 35 phenyl phosphite. There were removed 1280 parts of by reacting TPP with HBPA in the ratio of 2 mols to 3 mols.

distillate to give a solid resin.

TABLE 1 Phenols Out Hydroxyl (Mols) Molecular P, Atoms] Triads 11 Wt. of Molecule P, Percent Polymer Groups! N 0. Total Per 11 Molecule 4 4 964 2 6. 4 2 116 9 4. 5 1,834 4 6.7 3 91 14 4. 67 2, 704 6 6.8 4 82 19 4. 75 3, 574 8 6. 9 5 79 24 4. 80 4, 444 10 7. 0 6 76 29 4.83 5,314 12 7.0 7 74 34 I 4.85 6,184 14 7.03 8 72.8 39 4.86 7, 054 16 7. 03 9 71. 6 44 4.88 7,924 18 7. 04 10 70.8 49 4.89 8,794 20 7. 05 11 70. 2 54 4.91 9, 664. 22 7. 05 12 69.7 59 4. 91 10, 534 24 7. 05 13 69. 2 17 84 4. 94 14, 884 34 7. 1 18 67. 8 Cross linked 6. 0 7.98 0 0 Example 12 Example 15 The procedure of Example 11 was repeated but the distillation was continued until 1271 parts of distillate were collected. The still residue was a clear solid resin with a phosphorus content of 6.7%. This product is one of the preferred ones according to the invention.

Example 13 1 partof the resin prepared in Example 4 was mixed with 100 parts of vinyl chloride resin (Geon 103 Ep) to give a stabilized composition.

Example 16 I 2 parts of the resin of Example 4 were mixed with 100 parts of solid polypropylene (melt index 0.8).

Example 17 1 part of the resin prepared in Example 11 and 2 parts of barium-cadmium laurate were mixed with 100 0 parts of polyvinyl chloride and 50 parts of dioctyl phthalate to give a stabilized product.

Example 18 One part of the product of Example 12 was mixer! with parts of polypropylene (melt index 0.4).

R20 OR:

III

where R and R are alkyl, aryl or haloaryl and Q is residue of a dihydric phenol or hydrogenated dihydric phenol. In some of the compounds, at least two of R and R are alkyl. To prepare compounds having Formula III there can be reacted any of the triaryl phosphites or trialkyl phosphites set forth previously with any of the bisphenols or hydrogenated bisphenols set forth previously. Additionally, there can be used triaryl phosphites such as tris (p-nonylphenyl) phosphite, tris (m-ethylphenyl) phosphite, tris (p-t-octylphenyl) phosphite, tris (p-dodecylphenyl) phosphite, phenyl bis (pnonylphenyl) phosphite, tris (O-hexadecylphenyl) phosphite, tris (p-cyclohexylphenyl) phosphite, decyl bis (butylphenyl) phosphite, and bis (dodecyl) nonylphenyl phosphite. Usually a dialkyl or diaryl phosphite or an alkaline catalyst is also employed in an amount of 0.1 The compound of Formula III can also be prepared by reacting 1 mole of a bisphenol, e.g., bisphenol A, or a hydrogenated bisphenol, e.g., hydrogenated bisphenol A, with 2 moles of phosphorus trichloride and 4 moles of monohydric phenol, e.g., p-nonylphenol.

The compounds of Formula III are good stabilizers and antioxidants for natural rubber, synthetic rubber, e.g., butadiene-styrene copolymer, vinyl chloride resins, olefin polymers, e.g., polyethylene, polypropylene and ethylene-propylene copolymers and also are goo-d lubricants. They are excellent stabilizers for rigid vinyl chloride resins.

It has been found that the most hydrolytically stable and best compounds in Formula III are derivatives of hydrogenated bisphenol A. They are considerably superior to the corresponding compounds from bisphenol A although the latter are also useful. 7

Examples of compounds within Formula III are tetra phenyl bisphenol A diphosphite, tetra p-nonylphenyl bisphenol A diphosphite, tetra p-hexadecylphenyl bisphenol A diphosphite, tetra p-methylphenyl bisphenol A diphosphite, tetra decyl bisphenol A diphosphite, tetra dodecyl bisphenol A diphosphite, di decyl di phenyl bisphenol A diphosphite, tetra p-t-octylphenyl bisphenol A diphosphite, tetra -phenyl hydrogenated bisphenol A diphosphite, tetra p-nonylphenyl hydrogenated bisphenol A diphosphite, tetra p-octylphenyl hydrogenated bisphenol A diphosphite, tetra p-t-octylphenyl hydrogenated bisphenol A diphosphite, tetra m-methylphenyl hydrogenated bisphenol A diphosphite, tetra p-hexadecylphenyl hydrogenated bisphenol A diphosphite, tetra decyl hydrogenated bisphenol A diphosphite, di phenyl di decyl hydrogenated bisphenol A diphosphite, tetra dodecyL phenyl hydrogenated bisphenol A diphosphite, tetraphenyl di(4-hydroxy-3-methylphenyl) dimethyl methane diphosphite, tetraphenyl di(4-hydroxy 3-methylcyclohexyl) dimethyl methane diphosphite, tetra dodecylphenyl di(4-hydroxy-3methylphenyl) dimethyl methane diphosphite, tetraphenyl di(4-hydroxyphenyl) methyl methane diphosphite, tetraphenyl di(4-hydroxycyclohexyl) methyl methane diphosphite, tetra octyl di(4-hydroxycycl-ohexyl) methylrnethane diphosphite, tetra nonylphenyl di(4-hydroxyphenyl) methyl ethyl methane diphosphite, tetra nonylphenyl di(4 hydroxycyclohexyl) methyl ethyl methane diphosphite, tetra ethylphenyl di(4-hydroxy-3- methylphenyl) phenyl methane diphosphite, tetra methylphenyl di(4 hydroxy-3 -methylcyclohexyl) phenylmethane diphosphite, tetra octylphenyl di(4-hydroxyphenyl) methane diphosphite, tetra octylphenyl di(4-hydroxycyclohexyl) methane diphosphite, tetraphenyl di(4-hydroxyphenyl) sulfone diphosphite, tetra octadecyl di(4- hydroxyph enyl) sulfoxide diphosphite, tetra nonylphenyl di(4-hydroxyphenyl) sulfide diphosphite, tetra nonylphenyl di(3-hydroxyphenyl) dimethyl methane diphosphite, tetra octylphenyl di(3-hydroxycyclohexyl) dimethyl methane diphosphite, tetra phenyl tetrachlorobisphenol A diphosphite, and tetra nonylphenyl tetrachlorobisphenol A diphosphite.

Example 20 2 moles of tris (p-nonylphenyl) phosphite, 1 mole of bisphenol A and 0.04 mole of diphenyl phosphite were heated and the p-nonylphenol formed removed by distillation in a vacuum until two moles had been removed. The residue in the pot was tetra (p-nonylphenyl) bisphenol A diphosphite.

Example 21 p The procedure of Example 20 was repeated replacing the bisphenol A by hydrogenated bisphenol A to produce tetra (p-nonylphenyl) hydrogenated bisphenol A diphosphite.

Example 22 2 moles of triphenyl phosphite, 1 mole of hydrogenated bisphenol A and 0.03 mole of diphenyl phosphite were heated and the phenol formed removed by distilling in a vacuum until 2 moles of phenol were recovered. The product in the pot was tetra phenyl hydrogenated bisphenol A diphosphite.

Example 23 The procedure of Example 22 was repeated replacing the triphenyl phosphite by 2 moles of tris (p-t-octylphenyl) phosphite to produce tetra (p-t-octylphenyl) hydrogenated bisphenol A diphosphite.

Example 24 The procedure of Example 22 was repeated replacing the triphenyl phosphite by 2 moles of tris (p-n-octylphenyl) phosphite to produce tetra (p-n-octylphenyl) hy drogenated bisphenol A diphosphite.

In general the products of Formula III are liquids when the R and R groups are alkyl below 12 carbon atoms or the R and R groups are normal alkaryl having up to 9 carbon atoms in the alkyl portion.

An example of a mixed phosphite having Formula III is given below.

Example 25 2 moles of octyl diphenyl phosphite, 1 mole of hydrogenated bisphenol A and 0.03 mole of diphenyl phosphite are heated as in Example 22 to form the compound:

where S indicates that the ring is saturated.

Example 26 600 grams (2.5 moles) of hydrogenated bisphenol A, 2200 grams (10 moles) of p-nonylphenol, 1550 grams of triphenyl phosphite and 25 grams of sodium phenolate (catalyst) were heated and distilled in a vacuum for 1 hour and 40 minutes to remove the phenol formed. The temperature in the pot rose from 116 to C. during this time. The liquid residue in the pot was filtered off to recover tetrakis (p-nonylphenyl) hydro- 1240 parts of triphenylpbosphite, 1300 parts of isodecyl alcohol, 480 parts of hydrogenated bisphenol A and 15 parts of diphenyl phosphite were mixed and subiected to vacuum distillation. Terminal conditions were 181 C. and Torr. 1033 parts of distillate were removed from the reaction vessel in the process. The residue in the pot was treated with 6 parts sodium carbonate, .6 parts Attagel (silica gel) and 10 parts Hi-Flo filter aid. The mixture was filtered ed, the filtrate had the following properties R.I. 1.4891; sp. gr. 0.963, Acid No. 0.19, Color, A.P.H.A.'20. The filtrate was tetradecyl hydrogenated bisphenol A diphosphite. This compound can also be called tetra decyl bis (cyclohexylene) dimethyl methane diphosphite.

Example 28 Example 29 2 moles of triphenyl phosphite, 1 mole of 2,6,2',6- tetrachloro bisphenol A and 0.04 mole of diphenyl phosphite were heated and the phenol formed removed by vacuum distillation until 2 moles had been removed. The residue in the pot was tetraphenyl 2,6,2,6-tetrachlorobisphenol A diphosphite.

Example 30 The procedure of Example 29 was repeated using 2 moles of tris (p-nonylphenyl) phosphite in place of the triphenyl phosphite to obtain tetrakis (p-nonylphenyl) 2,6,2,6'-tetrachlorobisphenol A disphosphite as the product.

Example 31 The procedure of Example 29 was repeated using 2 moles of tris decyl phosphite in place of triphenyl phosphite to obtain tetrakis (decyl) 2,6,2,6-tetrachlorobisphenol A diphosphite as the product.

Example 32 2480 grams (8 moles) of triphenyl phosphite, 816 grams (4 moles) of Hocmt': CHzO (|3CH:OH

CH3 CH3 (2,2-dimethyl-3-hydroxypropyl ester of a1pha,alpha dimethyl beta hydroxypropionic acid) were heated with 21 grams of diphenyl phosphite in a vacuum until 8 moles of phenol were recovered. The residue in the pot was 0 e on. 0

This compound is useful as a stabilizer and antioxidant for natural rubber, synthetic rubber, e.g. butadienestyrene copolymer vinyl chloride resins, olefin polymers, e.g. polyethylene, polypropylene and ethylenepropylene copolymers.

A similarly useful product is obtained if the triphenyl phosphite employed in Example 32 is replaced by 8 moles of tris (p-nonylphenyl) phosphite or 8 moles of tris (p-toctylphenyl) phosphite or 8 moles of tris ,(decyl) phos- .phite.

The novel compounds of the invention having the formula where R and R are selected from the group consisting of alkyl of 8-18 carbon atoms, aryl and haloaryl and at least two of R and R are alkyl and Q is the divalent residue of a member of the group consisting of a dihydric phenol and a hydrogenated dihydric phenol.

R50 0H3 0R5 where R, is a monocyclic carbocyclic aryl group and R is alkyl of 8-18 Carbon atoms.

where R is alkyl of 8-18 carbon atoms.

4. Di(dialkylphospliito dichlorophenyl) isopropylidene wherein the alkyl grouphas 8-18 carbon atoms.

References Cited UNITED STATES PATENTS 2,643,265 6/1953 Toy 260930 3,037,608 7/1962 Friedman et a1. 260982 3,239,464 3/1966 Matson et al 260928 X CHARLES B. PARKER, Primary Examiner.

A. H. SUTTO, Assistant Examiner. 

1. A COMPOUND HAVING THE FORMULA 